Preparation of copper compound and product thereof

ABSTRACT

THE COMPOUND OF THE FORMULA:   ((4-(C12H25-),1-((-)O3S-)BENZENE)2 ---&gt; (H2N-CH2-CH2-NH2)2   CU(+2)   IS PRODUCED BY REACTING AN AQUEOUS SOLUTION OF P-DODECYLBENZENE SULFONATE WITH CUPRIC CHLORIDE AT 80 TO 90*C. TO FORM CUPRIC P-DODECYLBENZENE SULFONATE, WHICH IS REACTED IN METHANOL WITH ETHYLENE DIAMINE TO FORM ITS ETHHYLENEDIAMINE COPPER (II) P-DODECYLBENZENE SULFONTE. THE COMPOUND IS USEFUL AS AN AGRICULTURAL BACTERICIDE AND INSECTICIDE.

United States Patent Otfice US. Cl. 260-4381 2 Claims ABSTRACT OF THE DISCLOSURE The compound of the formula:

is produced by reacting an aqueous solution of p-dodecylbenzene sulfonate with cupric chloride at 80' to 90 C. to form cupric p-dodecylbenzene sulfonate, which is reacted in methanol with ethylene diamine to form his ethylenediamine copperfll) p-dodecylbenzene sulfonate. The compound is useful as an agricultural bactericide and insecticide.

This application is a continuation of application Ser. No. 846,222, filed July 30, 1969, now abandoned.

DETAILED DESCRIPTION OF INVENTION This invention relates to a method for preparing bactericides and insecticides for agricultural use, which is characterized by the formation of coordinated or chelated metal complexes.

The metal chelate is defined as a compound having heterocyclic structure which is composed of metal atom and polydentate ligands. The industrial applications of metal chelates are just at the beginning. At present, they are used in the scientific studies, for instance as a catalyst in biochemical studies or as the chelatemetry in the field of analytical chemistry. On the other hand, owing to their characteristic solubilities in water (some are very soluble and some are insoluble) and their characteristic stabilities, they have just opened the way of applications in softening hard water (ion exchanger), washing agent for various materials (masking effect for metal ion) and pigment such as phthalocyanine blue. However, little has been developed in the field of synthesis and industrial application of general organoor organo-high-molecular weight chelate compounds, excepting a few examples such as some kinds of agricultural chemicals. As a chemical having metal chelate, we know dithiocarbamate type bactericides, which are famous for their low solubility in water, such as salt of zinc or manganese and also know quinoline copper.

The inventor has studied for stabilizing the coordination compounds having bactericidal effect, especially on metal chelates. It has been confirmed that the salts composed of benzenesulfonic acid or one of its derivatives,

" 3,786,079 Patented Jan. 15, 1974 such as those substituted by alkyl, hydroxyl or halogens, and heavy metal complex obtained by adding such ligands as aliphatic and aromatic mono-, diamines, heterocyclic nitrogen containing compounds (pyridine, quinoline, acridine, etc.) or ethanolamine etc., have an excellent antibacteria and antiinsect effects. The inventor continued the study and has also confirmed that the salts, which are composed of one of the derivatives of benzenesulfonic acid substituted by amino, nitro, cyano or alkoxy (especially lower homologs) and metal complexes obtained from copper, zinc, nickel, mercury, tin, lead, iron, manganese ions by adding such organic ligands as ethylenediamine, trimethylamine, pyridine, quinoline, acridine, ethanolamine, thiourea etc., are also excellent bactericides and insecticides.

Some examples of the bactericides and insecticides found by the present invention are shown below with procedures for preparation and their effect on bacteria and insect.

(A) Metal complex salts having nitrogen containing ligands:

(1) p-dodecylbenzenesulfonic acid copper ethylenediamine chelate (2) p-hydroxy-rn-uonylbenzenesulfonic acid lead trimethylamine coordination compound (3) p-chlorobenzenesulfonic acid nickel pyridine coordination compound (4) p-methyl o chlorobenzenesullfonic acid manganese quinoline coordination compound (5) benzenesulfonic acid mercury acridine coordination compound (6) p-dodecylbenzenesulfonic acid tin ethylenediamine chelate (7) p-dodecylbenzenesulfonic acid iron trimethylamine coordination compound (8) p-nitroaniline-o-sulfonic acid copper ethylenediamine chelate (9) m-nitrobenzenesulfonic acid lead trimethylamine coordination compound (10) sulfanilic acid nickel pyridine coordination compound (ll) p-cyanobenzenesulfonic acid manganese quinoline coordination compound (12) sulfanilic acid mercury acridine coordination compound (13) p-methoxybenzenesulfonic acid tin ethylenediamine chelate (l4) m-nitrobenzenesulfonic acid iron trimethylamine coordination compound (B) Metal complex salts having oxygen and nitrogen containing ligands:

(1) p hydroxy o nonylbenzenesulfonic acid copper ethanolamine coordination compound (2) sulfanilic acid copper ethanolamine coordination compound (C) Metal complex salts having nitrogen and sulphur containing ligands:

(l) p-dodecylbenzenesulfonic acid zinc thiourea chelate (2) m-nitrobenzenesulfonic acid zinc thiourea chelate It is possible to obtain the similar compounds as those mentioned above with 0 -0 alkyl. groups.

3 EXAMPLE 1 Procedure for preparing p-dodecylbenzenesulfonic acid bis(ethylenediamine) copper(II) complex salt (see Reaction Formula 1).

Seven hundred and fifty grams of p-dodecylbenzenesulfonic acid sodium salt (containing water, purity: 60%) were dissolved in 3 liters of water. The solution was kept at temperatures between 80 and 90 C. on a waterbath and 110.8 g. of cupric chloride dissolved in 1.5 liters of water were dropped therein under vigorous stirring in one hour. After the dropping was completed, the mixture was further heated under stirring at the temperature for about 30 minutes and then was cooled and filtered. The precipitation thus obtained was dissolved in 1.5 liters of hot water and cooled to be recrystallized. Approximately 760 g. of moist refined product were obtained. The refined product was dissolved in 300 g. of methanol and the copper content of the solution was determined conductometrically. A necessary amount of methanol (30 g.) was added, then 1080 g. of solution containing 1.73% of copper was obtained. The solution was added with 35.4 g. of ethylenediamine (2 moles for one atom of copper), then the color of the solution changed from green to blue.

The above operations brought about 115 g. of 22% solution of p-dodecylbenzenesulfonic acid bis(ethylenediamine) copper-(II) complex salt. This solution having pH of 4.8 and specific gravity of 0.995 is usable as a commercial product.

EXAMPLE 2 Procedure for preparing p-dodecylbenzenesulfonic acid bis (thiourea) zinc complex salt (see Reaction Formula 2). Reaction Formula 2 Zn 2NaCl Eight hundred and seventy grams of p-dodecylbenzenesulfonic acid sodium salt (containing water, purity: 60%) were dissolved in 600 ml. of water. The solution was kept at temperatures between 85-95 C. on a waterbath and g. of zinc chloride dissolved in 250 ml. of water was dropped therein under stirring in about one hour and was heated further for 30 minutes and then cooled and filtered. The solid product was dissolved by adding approximately 500 ml. of hot water and then purified by recrystallization. Eight hundred and fifty grams of moist refined product was obtained. The refined product was dissolved in 250 g. of methanol. With an aliquot portion of this solution zinc was determined by the di-ammonium hydrogen phosphate method. A required amount (50 g.) of methanol was added to the main solution and then 1150 g. of solution containing 1.55% zinc was obtained. To the solution 47.0 g. of thiourea dissolved in 50 g. of methanol was added and then about 1200 g. of pale yellow colored solution containing 20% of p-dodec ylbenzenesulfonic acid bis (thiourea)zinc(II) complex salt was obtained. The solution having pH of 4.2 and specific gravity of 0.98 is usable as a commercial product.

The bactericidal efiects of the product are shown below.

Disease develop- 1 ABS and en denote dodecylbenzenesulfonic acid and ethylenediamine, respectively.

1 A solution containing 20% of the chemicals was diluted.

These tests were carried out at Blight Damage Laboratory, Gardening Experimental Station, Okitsu Branch, Ministry of Agriculture and Forestry, Shizuoka Prefecture, Japan by the following procedures. Three pots of Chinese Citrons budded 15 days before were used for the individual tests. The buds were sprayed with 500 ml. of the chemicals by use of a hand sprayer. After being air-dried the plants were inoculated with a suspension of Xanthomonas cityi ('Hasse) Dowson of concentration of 10 per ml. by spraying. The plants were kept in a greenhouse for one night and then placed out of doors for one month. After these treatments, the plants were examined for their attacked leaves. The degree of attack (disease development) were classified into four degrees, that is zero-three, and the grade of the disease development of the plants was calculated by the following formula.

Grade of disease development+= 3 N where, n n and n represent the numbers of the leaves attacked up to the corresponding degree, respectively,

and N represents the total number of leaves examined.

The insecticidal elfects of the product are shown below.

Survival percent These experiments were carried out in the experimental field of Sanyo Kagaku Co., Ltd., Koyoto, Jana. The insect tested was Tetranychus urticae Koch and the testing method was as follows.

Leaves of cucumber parasitized with Tetranychus urticae Koch were immersed in the test solution of the chemicals for 3 seconds and then transferred in Petri dishes. After 24 hours the number of survivals was de termined. Three observations were carried out for each Alkyl(Cg-C benzenesulfonic acid bis(ethylenediamine) 6 Eighteen grams of zinc chloride were dissolved in 100 ml. of water. Fifty grams of sulfanilic acid sodium salt dissolved in 500 ml. of warm water were dropped into the solution kept at temperatures between 60 and 70 C. After the dropping was completed in about 30 minutes, the mix- .copperCII) complex salt, has a comparable or superior ture was stirred at the same temperature for about 2 eifect of Morestan (6-methyl quinoxaline 2,3-dithiocarhours. The solution was concentrated by heating to apbonate). proximately 100 m1. and then cooled down to room tem- EXAMPLE 3 perature. The solid separated was filtered off and was re- Procedure for preparing m-nitrobenzenesulfonic acid 10 crystanlzed from a Small p p Water The y1.e1d was bis(ethylenediamine) zinc(II) complex salt (see Reaction hundred and fifty m11hgram of the i were Formula 3) dissolved in 50 ml. of water and was titrated with EDTA using EBT as an indicator in a buttered solution of pH of Formulfl 10. Thus zinc was determined. The total solid was dis- OzN 15 solved in 140 g. of water, thereby 166 g. of solution containing 1.50% of zinc was obtained. To this solution 4.6 Z110 6 0 g. of ethylenediamine was added. Through these opera- I tions 171 g. of a pale yellow colored solution containing OHN v 10.6% sulfanilic acid bis(ethylenediamine) zinc(II) complex salt was obtained. This solution of pH of 6.0 and Q Q mo specific gravity of 1.110 will be put on market.

(In The other chelate and or coordination complex salts of copper, nickel, mercury, tin, lead, iron, and manganese (II) 2HgN-CHg-CHz-NH2 can be prepared by the following procedures. Heavy metal HgG--OH, salts of organic sulfonic acid, such as sulfanilic, nitro- 0,: 2 11 1 N02 benzenesulfonic, cyanobenzenesulfonic and methoxybenzenesulfonic acid, etc., were obtained from corresponding G inorganic salts of Cu Ni Sn Hg Pb Fe and Mn HZN NHZ The metal salts thus obtained are reacted with compounds H2 H2 which make coordination bonds with metal such as those containing nitrogen (monoamine, diamine, pyridine, Seventeen grams of zinc carbonate was suspended in quinoline, acridine, etc.), those containing oxygen and 170 ml. of water and 50 g. of m-nitrobenzenesulfonic acid nitrogen (ethanolamine etc). and those containing nitrodissolved in 500 ml. of warm water was dropped therein gen and sulphur (thiourea etc.). and the mixture was kept at temperatures between 80 and In the ways mentioned above, it is possible to prepare 85 C. under agitation. The dropping was completed withvarious kinds of chelate or coordination compounds in in about 30 minutes and the mixture thus formed was the categories of A, B and C. stirred further for about 2 hours at the temperature. While Comparison tests for anti-bacterial property made on the mixture was warm, unreacted solids were filtered 01f the compounds of Examples 3 and. 4 are summarized in and the filtered solution was cooled down to room temthe following table.

Concentra- Corrected tion of Number Average ungermetal of spore percent of minated,

Chemicals tested (ppm) examined germinated percent Sulfanilic acid zinc salt (reference).-- 16. 3 314 59. 0 36. 9 Sulfanilic acid bis(ethy1enediamine) zinc(II) complex sa1t...--. 15. 7 315 26. 3 71. 9 m-Nitrobenzenesulfonic acid zinc salt (reference) 16. 0 322 56. 0 40. 1 m-Nitrobenzenesulionic acid bis(ethylenediamine) zinc(II) complex salt 14. 4 309 29. 6 68. 3 Mercurie chloride (reference) 2. 5 317 44. 7 54. 6 Untreated. 306 98. 5

Average of 3 observations. perature. Thirty grams of white crystalline product was These examinations were carried out in the laboratory obtained. With precisely 150 mg. of the material, zinc of Sanyo Kagaku Co. Ltd., Kyoto, Japan. was determined by the chelate titration. The total crystal Examination method: Conidia of Helminthosporium was dissolved in 190 ml. Of Water and 220 g. Of 801011011 oryzae Breda et Haan were, prepared by culturing 01 an containing 1.50% of zinc was obtained. To this solution agar plate media f potato containing f dextrose 6.1 g. of ethylenediamine was added. Through these opera- (PDA) f r 7 days at C. lions 226 a Pf Yellow 9 A conidia suspension in sterilized distilled water was benzenesulfomc ac d b1s(ethylened1am1ne) zmc(II) comprepared and it was filtered through a cotton gauze Then Flex. salt obtamed' T prolhlct of PH of and the suspension was centrifuged twice at 1000 rpm. for 2 speclfic gravlty of Is a usabp proguctt minutes. The concentration of conidia was adjusted to 10 lfrocedine for preparmg sulfamhc blsmthylenedl' per ml. (determined by aThomas globle counter). To this amine) z1nc(II) complex salt (see Reaction Formula 4). suspension 01% of dextrose was added. Ream A drop of 0.05 ml. of the test solution was placed on 21101, zmN -S0Na a slide glass. After air-dried, 0.05 ml. of the conidia suspension was dropped on it. The glass was brought into a H NS0;Zn0;S-- 2mm wet Petri dish kept for 20 hours at 28 C.

The number of germinated and ungermmated conidia (m were determined under a microscope. Corrected following (II) ZH N-CHz-CHz-NH: equation.

H1CCHI H,N NH, Corrected ungerminated percentage= X 100 KING-S0;- ai -0aszen,

a; germinated percent for untreated section H b; germinated percent for treated section.

7 What is claimed is: 1. A compound of the formula 2. A process for the production of the compound of claim 1, which comprises reacting an aqueous solution of p-dodecylbenzene sulfonate with cupric chloride at 80 to 90 C. to form cupric p-dodecylbenzene sulfonate, which is reacted in methanol with ethylene diamine to form bis ethylenediamine copper-(II) p-dodecylbenzene sulfonate.

References Cited UNITED STATES PATENTS 2,864,742 12/1958 Whetstone et a1. 260-4381 2,455,687 12/1948 Liberethson 260-4381 2,897,114 7/1959 Sauls 424 494- 2,924,552 2/1960 Harwood 424-494 2,928,856 3/1960 Harv/66d" 424+294; 2,977,279 3/1961 Kosmin 424-294 FOREIGN PATENTS 1,057,106 5/1959 Germany 424-294 OTHER REFERENCES 9 Black, Aust. J. Chem., vol. 20, pp. 2275-2277 (1967).-

HELEN M. s. SNEED, Primary Examiner. V 

